Metal compounds of azo dyestijffs



Patented Nov. 12, 1940 UNITED STATES METAL COMPOUNDS OF AZO' DYE'STUFFS Max Schmid, Riehen, near Basel, Switzerland, as-

signor to the firm Society of Chemical Industry in Basie, Basel, Switzerland N0 Drawing;

Original application September 27,

1937, Serial No. 166,021. Divided and this application March 23, 19

39, Serial No. 263,796. In

Switzerland October 3, 1936 l 11 Claims. (01. 260-117) This is a division of my application for patent Serial No. 166,021, filed in U. S. A. on September 27, 1937, and in Switzerland on October 3, 1936, of which the following is a full, clear and exact specification.

According to this invention valuable products are obtained by treating with an agent yielding metal, such as a compound of copper, chromium, nickel, iron or cobalt, in substance or on the fibre, an azo dyestufi which is obtainable by the action of such a diam-compound of the benzene and naphthalene series which contains in orthoposition to the diazo-group a substituent which is capable of forming stable lakes with the azogroup formed, such as an ortho-hydroxy or ortho-carboxyl-diazo compound on a 1-aryl-5- pyrazolone which itself is obtainable by condensation of a pecarbonyl-carboxylic acid ester with a hydrazine of the general formula S 0311 S 03H in which y represents a -CH=CH-group or a --CH2-CI-I2-group and 2 represents a group which is formed by reduction of a nitro-group in combination with a condensation, such as an azoor azoxy-group or an amino-group substituted by the residue of an organic acid. The new azo dyestuffs containing metal thus obtained are distinguishd by the high fastness to light of their dyeings and by their excellent affinity for vegetable fibres, such as cotton, flax, ramie, and for fibres of regenerated cellulose, such as artificial silks, for example viscose artificial silk or cuprammonium artificial silk.

Among the ortho-hydroxy and ortho-carboxydiazo compounds which come into consideration for the preparation of the azo dyestuffs forming the parent materials of the invention there may be named quite generally those derived from ortho-aminopheno1s or ortho-aminonaphthols or from ortho-aminocarboxylic acids of the benzene or naphthalene series, for example l-hydroxy-Z-aminobenzene, l-hydroxy-Z-arnino-- chlorobenzene, 1hydroXy-2-amino-4-nitrobenzene, 1-hydroxy-2-amino-5nitrobenzene, l-hydroxy-Z-amino-4 G-dinitrobenzene, l-hydroxy- 2-amino-5-nitro-6-chlorbenzene, l-hydroxy-2- amino-i-methyl-benzene, 1-hydroXy-2-amino-4- nitro-S-chlorbenzene, l-hydroxy-Z-amino--nitrobenzene-fi-sulfonic acid, 1-hydroxy-2-amino- 6-nitrobenzene-4-sulfonic acid, l-hydroxy-Z- aminobenzene-i-sulfamide, l-hydroxy-Z-aminonaphthalene-4 B-disulfonic acid, 2-hydroxy-1- arninonaphthalene-4-sulfonic acid, 2-hydroxy-1- amino-6-nitronaphthalene-4-sulfonic acid, 1-

aminobenzene-Z carboxylic acid, chlorbenzene-2-carboxylic acid, 'l-'-amino-4-nitrobenzene-Z-carboxylic acid, 1-amino-4-benzoylamino-Z-carboxylic acid, 4-amino-3-carboxylic-aZmbenZeneA-suIfonic acid, aminosulfobenzoic acid (NI-1221,}COOHI2, SOzHi lhZ-aminonaphthalene-tS-carboxylic acid, and so on.

Among the p-carbonyl-carboxylic acid esters available for preparing the 1-aryl-5-pyrazolones which can be. used for the synthesis of the parent dye stuffs there may be named forr'nyl acetic acid esters, furthermore B-keto-carboxylic acid esters, such as ethyl-aceto-acetate, ethyloxal acetate, ethylbenzoylacetate, terephthaloyldiacetic acid ethyl ester, and so on.' Among the hydrazines which likewise are used for preparing the 1-aryl-5-pyrazolones used for the synthesis of the arent dyestuffs there may be named such products as: i

l-aminoi- Quite generally, however, it is more advantageous I first to combine the nitrohydrazine or the aminohydrazine with one of the aforesaid fi-carbonylcarboxylic acid esters and then to conduct the reduction of the nitro-group in combination with a condensationlreaction. This may occur, for example, by crape-sugan'the course of the reaction being presumed to consist in the reduction of a part of the product to the amino-group, which then condenses'with' the unreduced or only partially reduced portions to'produce an azo or azoxy compound (compare Formulae 8 and 10 below which is the particular subject of the present application); or the operation may consist in complete reduction of the nitro-group to the NI-IzglOllp and subsequent condensation, for example with a halogen compound which converts the NHz-group into a NH-(|Jb-group in which a stands for metalloid whose atomic weight is not less than 14 and not greater than 16, and 1) stands for an organic residue of the aliphatic, aromatic, cycloaliphatic, heterocyclic, (2) I N H=CH N02 5 araliphatic series and so on. Such products con- 5 stitute acyl derivatives or the amidines which [I SOaH SOaH chemically are closely related thereto. As is 0 known, the introduction of such residues into intermediate products or dyestuffs increase the GHQ affinity for vegetable fibre. Such residues can (JEN I 10 be introduced by acylation, for example by treatment with benzoyl chloride, phenylacetyl chlo- (3) I ride, cinnamyl chloride, succinyl chloride, butyryl E I chloride, hexahydrobenzoyl chloride, furane-car- I 503E 803B boxylic acid chloride, benzimino ether, by treat- 15 ment with phosgene which is the particular subject of the parent application Serial No. 166,021, 0 filed Sept. 27, 1937 orthiophosgene or by treat- H ment with heterocyclic products of the nature of amidine halides, such as cyanuric acid chlo- (4) I N OH=CH N02 20 ride, cyanuric acid bromide, tribromopyrimidine, I

2:6 -,dichloro 4 methylpyridine, dichloroquinazoline, and so on. The manufacture of such products containing heterocyclic rings is the par- 5 ticular subject of my co-pending application Serial No. 268,795, filed March 23, 1939, which copending application is also a divisional application of my parent application Serial No. 166,- 021, filed September 27, 1937. CH3 Particularly valuable products result when the =N 30 c 7 condensation is conducted in such a manner that (5) 011:0]; the residue 1) 15 so constituted that-1t contains an azochromophore or is adapted to couple with HZ O II 30311 SOaH diazo compounds to produce azodyestufis. 0 There are thus obtained 1-ary1-5-pyrazolonies 35 in which the and residue has the general for- I mula: I COOH (6 N CH=CH NH 40 scan 03H I Q Q 2 40 I in which y stands for a I I 50311 503B CH=CH- or a -CI-IzCHz- 45 group andz stands for a Intro-group in combination with a condensation. Such pyrazolone derivatives are, for example:

CH: C=N I I 50 (1 NQ0H=0H N01 1 /N OH=CH NH; H2 -C H: C I

II S0311 S0311 SOJH SOaH I 0 O l V 55 (EH3 I 10113 I; (8 C=N\ V /N=C I /N CH=OH N=N CH=CH N\ I Hie-c CCH n s 03151 S 03H s 03H s 0311 Il I 0H3 (1H3 o) I I /NQOH=OH N=N CH=CHN\ I 65 'Hic-o c-oHi I] S 0211 S 03H S 03H S 03H I] 0 0 (RH: E I 70 (10) I /N 5CH=OHON=N(IE(HJ H2CC 11 o in Formulae 5-10, all of which are given by way of example, it is evident how numerous are the intermediate products for making the dyestuffs forming the parent materials for the invention;

'group during metallisation) or a COO-alkylgroup which is then 'saponified to a COOH-group. The metallization can also occur simultaneously with the coupling of the azo dyestuff; this procedure is particularly to be recommended in the production of copper compounds.

The new dyestuffs, therefore, are complex metal compounds of dyestuffs such as the folregard must further be had to the fact that the lowing:

CH3 (EH:

t=N N=C OOOH H000 N oH=oH N=N CH=CH N Q C} Q l N=NCC ll soiH SOaH SOaH 80311 n a H 0 H in which R stands for an aromatic nucleus of the benzene or naphthalene series, 1' stands for an OH- or a COOI-I-group which stands in orthoposition to the -N=N-group, 1; stands, for instance, for hydrogen, alkyl,aryl, COOH or COOR (R'=alkyl), y for a CH=CH- or a CH2CH2 group, and z for a N02- or NI-Iz-group, and then to proceed with the conversion of the nitroor amino-group.

The combination of the aforesaid coupling components and diazotized ortho-hydroxylated or ortho-carboxylated diazotization components to produce azo dyestuffs proceeds, as is usual for pyrazolones, in an acid or an alkaline medium.

The conversion of the azo dyestuffs into metal compounds may as a. rule be conducted by treatment of the finished dyestufi with a salt, hydroxide or oxide of one of the metals hereinbefore referred to, for example copper sulfate, copper chloride, copper hydroxide, ammoniacal copper oxide, copper tetramine sulfate, derivatives of copper tetramine sulfate in which the ammonia residues are replaced by the residues of organic bases, such as methylamine or pyridine, chromium chloride, chromium sulfate, chromium fluoride, chromium formate, chromium acetate, chromium hydroxide, sodium chromite, sodium glycerine chromite, nickel chloride, nickel sulfate, cobalt chloride, manganese chloride, and so on. The metallisation may be conducted on the fibre or advantageously in substance by treating or Warming a'solution or suspension of the dyestuff in admixture with one of the aforesaid salts in an open vessel or under pressure. The

same metalliferous dyestuffs can also be obtained by metallising dyestuffs which have been pre pared from the 1-aryl-5-pyrazolones here in question and from diazotization components which contain no OI-I- or COOH-group in ortho-position but contain in ortho-position a substituent which in the course of the metallisation becomes converted into an OH or COO-group, such as a. chlorine or bromine atom or an OClh-group (which substituents are converted into the OH- SOaH SOaH in which :1: stands for a substituent in ortho-positio-n to the N=N-group which is capable of forming complex compounds with metals, Py stands for the residue of a E-pyrazolone which is combined in l-position with the residue SOaH S0311 and in 4-position with the azo-residue, y for a CH=CH- or a CH2-CI-Iz-group and z for the conversion product of a nitro-group.

The characteristic properties of the new metalliferous dyestuffs are conditioned by the grouping S0311 sons which in particular is responsible for the shade of the dyestuffs, their high fastness to light and their afiinity for vegetable fibres, as will be evident from a comparison of the properties of the individual products described in the examples which follow.

When prepared in substance the new products constitute in the dry state yellow to brown or blackish powders which are soluble in water to yellow to orange, brown, greenish, olive and blackish solutions from which they are adsorbed by cellulose fibres yielding dyeings of similar shades which are distinguished by their excellent properties hereinbefore referred to. Details in respect of the manufacture of such dyestuffs and of their properties will be found in the following examples, the number of which could be multiplied as desired. The parts in the examples are by weight.

. Example 1 13.? parts of 1-aminobenzene-Z-carboxylic acid are diazotized in the usual manner and coupled in an acetic acid medium with 45.1 parts of the 3-methyl-5-pyrazolone of the formula S 03H S 0311 C=N The dyestuff is isolated, dissolved in 1000 parts of water, containing an excess of sodium carbonate, and the solution is treated with phosgene at 40-50 C. When this treatment is ended, that is to say when a free amino-group is no longer present, the dyestuff is isolated and dried. It is a yellow powder which dyes cotton fast yellow shades.

vThe dyestufi thus prepared is suspended in 3000 parts of: water and the suspension is mixed with an ammoniacal copper oxide solution corresponding with parts of crystallized copper sulfate. The whole is stirred at 60-'70 C. for about 1 hour, whereupon the metalliferous dyestuff is filtered with suction and cautiously dried. The dry dyestufi containing copper is a brown powder which dyes vegetable fibres and artificial silks of regenerated cellulose excellent yellow shades fast to light. The non-metallised dyestuff corresponds thus to the formula The conversion of the dyestufi into its copper complex may also be conducted in an acid medium by treatment with a copper salt such as copper sulfate. I

By combining the diazo compound from 13.7 parts of 1-amino-benzene-2-carboxylic acid with 45.3 parts of the 3-methyl-5-pyrazolonone of the formula soar: $0311 treating the dyestuff with phosgene and convert- SOaH O=N ing the product into the complex copper compound as above described there is obtained a dyestuff containing copper which, when dried, constitutes a yellow-brown powder and dyes cotton fast yellow shades, resembling in shade and properties those of the stilbene product.

By suspending 59.9 parts of the dyestuff described in the first paragraph of this example in about 3000 parts of water and treating the suspension with a solution of 30 parts of crystallized nickel sulfate in 200 parts of Water for 1 hour at YO-80 C. in the presence of sodium acetate there is obtained the complex nickel compound of the dyestufi which, when dried, is a brownish powder which dyes cotton fast yellow shades with a somewhat orange hue.

The same shades are obtained by first dyeing with the non-metallized dyestuff in the manner usual for dyeing with direct dyestuffs and then after-coppering or after-treating the dyeing with a nickel salt. By treating with an iron salt a dyeing prepared with an alkali salt of the dyestuff there is obtained a dull yellow shade, by treatment with a cobalt salt a yellow shade, with a chromium salt a somewhat greenish-yellow shade and with a manganese salt a yellow shade.

Example 2 I 48.1 parts of the 3-methyl-5-pyrazolone of the formula are dissolved in 300 parts of water and 11 parts of sodium carbonate and coupled with the diazo compound prepared as usual from. 13.7 parts of anthranilic acid. The dyestufi is isolated and re-. duced in an aqueous suspension at 50-60 C. with a solution of 21 parts of dextrose and 25' parts of caustic soda solution of 36 Be. The brown-red dyestuff thus formed is isolated; it is presumed to contain the azoxyor azo-group and to have the formula SOsH S0311 SOaH 00011 I I I I I orange shades.

or the formula OOOH | S 02H S 0:15 N=N--G= N CH=OH N SOaH 03H inwhich R stands for a nucleus of the group consisting of aromatic nuclei of the benzene and naphthalene series, :1: stands for a lake-forming group, Py stands for the radical of a S-pyrazolone which is combined in l-position with the radical and in 4-position with the azo-group, y stands for a connecting link of the group consisting of --CH=CH- and -CI-I2--CH2--, and z for a radical comprising at least one nucleus of the group consisting of nuclei of the benzene and naphthalene series united to the radical SOaH SOaH by a connecting link selected from the groups consisting of azo and azoxy groups, which products form yellow to brown powders, dissolve in water to yellow to orange, brown and olive solutions, and dye cotton fast yellow to orange, brown and olive tints which are particularly fast to light. 2. The metal compounds of the azo dyestuffs having in the free state the general formula in which R stands for a nucleus of the group consisting of aromatic nuclei of the benzene and naphthalene series, :1: stands for a lake-forming group, which is combined in l-position with the radical ar on-9% 808K 0311 and in i-position with the azo-group, 2 stands Py stands for the radical of S-pyrazolone for a radical comprising at least one nucleus of SOaH the group consisting of nuclei of the benzene and naphthalene series united to the radical OaH by a connecting link selected from the groups consisting of azo and azoxy groups, which products form yellow to brown powders, dissolve in water to yellow to orange, brown and olive solutions, and dye cotton fast yellow to orange, brown and olive tints which are particularly fast to light. 3. The copper compounds of the azo dyestufis having in the free state the general formula in which It stands for a nucleus of the group consisting of aromatic nuclei of the benzene and naphthalene series, a: stand for a lake-forming group, Py stands for the radical of a 5-pyrazolcne which is combined in l-position with the radical SOsH SOsH and in l-position with the azo-group, y stands for a connecting link of the group consisting'of --CI-I=CH and CH2--CH2, and z fora radical comprising at least one nucleus of the group consisting of nuclei of the benzene and naphthalene series united to the radical.

SOBH I SOaH by a connecting link selected from the groups consisting of azo and azoxy groups, which products form yellow tobrown powders, dissolve in water to yellow to orange, brown and olive solutions, and dye cotton fast yellow to orange, brown and olive tints which are particularly fast to light.

4. The copper compounds of the azo dyestuffs having inthe free state the general formula in which R stands for a nucleus of the group consisting of aromatic nuclei of the benzene and naphthalene series, a: stand for a lake-forming group, Py stands for the radical of a 5-pyrazolone ill which is combinedin l-position with the radical and in 4-position with the azo-group, 2 stands for a radical comprising at least one nucleus of o the group consisting of nuclei of the benzene and naphthalene seriesunited to the radical by a connecting link selected from the groups consisting of azo and azoxy groups, which products form yellow to brown powders, dissolve in water to yellow to orange, brown and olive solutions, and dye cotton fast yellow to orange, brown and olive tints which are particularly fast to light.

5. The metal compound of the azo dyestufis having in the free state the general formula is combined in l-position with theradical 7. The copper compounds of the azo dyestuifs having in the free state the general formula I SOsH SOaH $0311 in which R1 and R2 stand for nuclei of the group consisting of aromatic nuclei of the benzene and naphthalene series, :1: stands fora lake-forming group in ortho position to the -N==N-group, Py

z V x s0=H S0311 in which R1 and R2 stand for nuclei of the group consisting of aromatic nuclei of the benzene. and naphthalene series, as stands for a lake-forming group in ortho position to the N=N-group, Py stands for the radical of a 5-pyrazolone which is combined in l-position with the radical OaH $0311 and in 4-position with the azo-group, y stands for a connecting link of the group consisting of CH=CH and CH2CH2-, and z for a connecting link selectedfrom the group con-.

sisting of the azo group and the azoxy group,

which products form yellow to brown powders, dissolve in water to yellow to orange, brown and olive solutions, and dye cotton fast yellow to S 0 3H I SOaH orange, brown and olive tints which are particularly fast to light.

6. The metal compounds of the azo dyestuffs having in the free state the general formula SOaH soar:

" in which R1 and R2 stand for nuclei of the group consisting of aromatic nuclei of the benzene and naphthalene series, :1: stands for a lake-forming group in ortho position to the -N=N-group, Py stands for radical of a 5-pyrazolone which dOaH stands for the radical of a 5-pyrazolone.which is combined in l-position with the radical Q Q SOaH tom and in 4-position with the azogroup, y stands for a connecting link of the group consisting of -CH=CH and -CH2CH2, and z for a connecting link selected from the group consisting of the azo and the azoxy group, which products form yellow to brown powders, dissolve in water to yellow to orange, brown and olive solutions, and dye. cotton fast yellow to orange,

brown and olive tints which are particularly fast to light.

8. The 'copper compounds of the azo dyestufis having in the free state the general formula PyN=N-R= SOaH SOEH in which R1 and R2 stand for nuclei of the group consisting of aromatic nuclei of the benzene and naphthalene series, at stands for a lake-forming group in ortho position to the --N=N-group, Py

SOaH

stands for the radical of a 5-pyrazolone which is combined in 1-position with the radical SQzH n SOeH and in 4-position with the azo-group, z stands for a connecting link selected from the group COOH COOH

9. The copper compounds of the azo dyestufis having in the free state the general formula 03H SOIH in which Py stands for the radical of a -pyrazolone which is combined in l-position with the radical SOIH S 03H and in 4-position with the azo-group, y stands for a connecting link of the group consisting of -CH=CH- and --CI-Iz-CH2, and 2 stands for a connecting link selected from the groups consisting of azo and azoxy groups, which prod- 45 ucts yield orange tints on the vegetable fiber which are fast to light,

10. The copper compounds of the azo dyestufis having in the free state the formula N=N- -o l 1 II SOBH 0,13 01H can I in which 2 stands for a connecting link selected from the groups consisting of azo and azoxy groups, which product yields on the vegetable fiber yellow tints fast to light.

11. The copper compounds of the azo dyestuffs having in the free state the general formula OOOH S OaH 0111 S OgH 03H razolone which is combined in l-position with the radical QCH=CHO SOaH SOaH and in 4-position with the azo-group, 2 stands for a connecting link selected from the groups consisting of azo and azoxy groups, which products yield orange tints on the vegetable fiber which are fast to light.

MAX SCHMID. 

